Methods for depositing a titanium aluminum carbide film structure on a substrate and related semiconductor structures

ABSTRACT

Methods for depositing a titanium aluminum carbide (TiAlC) film structure on a substrate are disclosed. The methods may include: depositing a first TiAlC film on a substrate utilizing a first cyclical deposition process, and depositing a second TiAlC film over the first TiAlC film utilizing a second cyclical deposition process. Semiconductor structures including titanium aluminum carbide (TiAlC) film structures deposited by the methods of the disclosure are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Non-provisional of, and claims priority to and the benefit of, U.S. Provisional Patent Application No. 63/064,275, filed Aug. 11, 2020 and entitled “METHODS FOR DEPOSITING A TITANIUM ALUMINUM CARBIDE FILM STRUCTURE ON A SUBSTRATE AND RELATED SEMICONDUCTOR STRUCTURES,” which is hereby incorporated by reference herein.

FIELD OF INVENTION

The present disclosure relates generally to methods for depositing a titanium aluminum carbide (TiAlC) film structure on a substrate and particularly to methods for depositing a TiAlC film structure utilizing two or more cyclical deposition processes. The present disclosure is also related generally to semiconductor structures including a TiAlC film structure deposited by two or more cyclical deposition processes.

BACKGROUND OF THE DISCLOSURE

Cyclical deposition processes, such as, for example, atomic layer deposition (ALD) and cyclical chemical vapor deposition (CCVD), sequential introduce two or more precursors (reactants) into a reaction chamber wherein the precursors react with the surface of a substrate one at a time in a sequential manner. Cyclical deposition processes have been demonstrated which produce films with excellent conformality.

However, as film thicknesses decrease in next generation device nodes, ever more accurate thickness control of deposited films is desirable to achieve efficient semiconductor device structures.

Accordingly, cyclical deposition methods for depositing films with a high degree of thickness control are highly desirable.

SUMMARY OF THE DISCLOSURE

This summary is provided to introduce a selection of concepts in a simplified form. These concepts are described in further detail in the detailed description of example embodiments of the disclosure below. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

In some embodiments, methods for depositing a titanium aluminum carbide (TiAlC) film structure on a substrate are disclosed. The methods may comprise: depositing a first TiAlC film on the substrate utilizing at least one first unit deposition cycle of a first cyclical deposition process at a first growth rate per cycle (GPC), and depositing a second TiAlC film over the first TiAlC film utilizing at least one second unit deposition cycle of a second cyclical deposition process at a second growth rate per cycle, wherein the first growth rate per cycle is greater than the second growth rate per cycle.

For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein above. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

All of these embodiments are intended to be within the scope of the invention herein disclosed. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures, the invention not being limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the invention, the advantages of embodiments of the disclosure may be more readily ascertained from the description of certain examples of the embodiments of the disclosure when read in conjunction with the accompanying drawings, in which:

FIG. 1 illustrates a non-limiting exemplary process flow, demonstrating a method for depositing a titanium aluminum carbide (TiAlC) film structure according to embodiments of the disclosure;

FIG. 2 illustrates a non-limiting exemplary process flow, demonstrating a first cyclical deposition process for depositing a first TiAlC film according to embodiments of the disclosure;

FIG. 3 illustrates a non-limiting exemplary process flow, demonstrating a second cyclical deposition process for depositing a second TiAlC film according to embodiments of the disclosure; and

FIGS. 4A-4D illustrate simplified cross-sectional diagrams of semiconductor structures including titanium aluminum carbide (TiAlC) films and film structures according to the embodiments of the disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

The illustrations presented herein are not meant to be actual views of any particular material, structure, or device, but are merely idealized representations that are used to describe embodiments of the disclosure.

As used herein, the term “substrate” may refer to any underlying material or materials that may be used, or upon which, a device, a circuit, or a film may be formed.

As used herein, the term “cyclical deposition” may refer to the sequential introduction of precursors (reactants) into a reaction chamber to deposit a film over a substrate and includes deposition techniques such as atomic layer deposition and cyclical chemical vapor deposition.

As used herein, the term “cyclical chemical vapor deposition” may refer to any process wherein a substrate is sequentially exposed to two or more volatile precursors, which react and/or decompose on a substrate to produce a desired deposition.

As used herein, the term “atomic layer deposition” (ALD) may refer to a vapor deposition process in which deposition cycles, preferably a plurality of consecutive “unit deposition cycles,” are conducted in a reaction chamber. Typically, during each cycle, the precursor is chemisorbed to a deposition surface (e.g., a substrate surface or a previously deposited underlying surface such as material from a previous ALD cycle), forming a monolayer or sub-monolayer that does not readily react with additional precursor (i.e., a self-limiting reaction). Thereafter, if necessary or desired, a reactant (e.g., another precursor or reaction gas) may subsequently be introduced into the process chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. Typically, this reactant is capable of further reaction with the precursor. Further, purging steps may also be utilized during each cycle to remove excess precursor from the process chamber and/or remove excess reactant and/or reaction byproducts from the process chamber after conversion of the chemisorbed precursor. Further, the term “atomic layer deposition,” as used herein, is also meant to include processes designated by related terms such as, “chemical vapor atomic layer deposition”, “atomic layer epitaxy” (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of precursor composition(s), reactive gas, and purge (e.g., inert carrier) gas.

As used herein, the term “film” and “film structure” may refer to any continuous or non-continuous structures and material deposited by the methods disclosed herein. For example, “film” and “film structure” could include 2D materials, nanorods, microlaminates, nanolaminates, nanotubes, or nanoparticles or even partial or full molecular layers or partial or full atomic layers or clusters of atoms and/or molecules. “Film” and “film structure” may comprise material or a layer with pinholes, but still be at least partially continuous.

As used herein, the term “metalorganic” or “organometallic” are used interchangeably and may refer to organic compounds containing a metal species. Organometallic compounds may be considered to be subclass of metalorganic compounds having direct metal-carbon bonds.

As used herein, the term “metalorganic aluminum precursor” may refer to organic precursors containing an aluminum species.

As used herein, the term “growth rate per cycle” or “GPC” may refer to the average thickness of material deposited during a unit deposition cycle of a cyclical deposition process and is commonly expressed in the units Angstroms per cycle (A/cycle).

In the specification, it will be understood that the term “on” or “over” may be used to describe a relative location relationship. Another element or layer may be directly on the mentioned layer, or another layer (an intermediate layer) or element may be intervened therebetween, or a layer may be disposed on a mentioned layer but not completely cover a surface of the mentioned layer. Therefore, unless the term “directly” is separately used, the term “on” or “over” will be construed to be a relative concept. Similarly to this, it will be understood the term “under”, “underlying”, or “below” will be construed to be relative concepts.

A number of example materials are given throughout the embodiments of the current disclosure, it should be noted that the chemical formulas given for each of the example materials should not be construed as limiting and that the non-limiting example materials given should not be limited by a given example stoichiometry.

The present disclosure includes methods for depositing titanium aluminum carbide (TiAlC) film structures and related semiconductor device structures including such titanium aluminum carbide (TiAlC) film structures. As a non-limiting example, the TiAlC film structures of the present disclosure may be utilized as at least a portion of a metal gate stack. In some embodiments of the disclosure, TiAlC film structures may be deposited by utilizing two or more cyclical deposition processes, such as, for example, atomic layer deposition processes or cyclical chemical vapor deposition processes.

Current metallic films (e.g., pure metals, metal silicides, metal nitrides, metal carbides, etc.) employed in metal gate stacks may have limitations due to their unsuitable effective work function values. For example, it is known that the effective work function of a film may vary as a function of its thickness. Therefore, as device geometries decrease in advance technology node applications, the thickness of the corresponding device films, such as the metallic film(s) of the metal gate stack, may also decrease with an associated change in the effective work function of an associated transistor gate stack. Such a change in the effective work function of the gate stack may result in a non-ideal effective work function for both NMOS and PMOS device structures. Deposition methods and the associated semiconductor device structures are therefore desired for forming metal gate stacks with a preferred work function. Examples of such deposition methods and semiconductor device structures are disclosed in further detail herein.

In addition, the present disclosure also generally includes methods for depositing TiAlC film structures with a higher order of thickness accuracy by employing two or more TiAlC cyclical deposition processes with differing deposition parameters. In more detail, for a given set of fixed cyclical deposition process parameters, a cyclical deposition process may deposit a film at a substantially constant growth rate per cycle (GPC), commonly given in units of Angstroms per cycle (Å/cycle). However, as next generation device structures necessitate device films with ever reduced thickness, a single cyclical deposition process may deposit a film at a GPC which is non-ideal for the desired thickness required for the device film. Accordingly, methods are desirable for depositing TiAlC film structures utilizing two or more TiAlC cyclical deposition processes, wherein subsequent cyclical deposition processes deposit a TiAlC film at a different growth rate per cycle, thereby enabling a higher order of film thickness accuracy.

Therefore, the embodiments of the disclosure may comprise methods of depositing a titanium aluminum carbide (TiAlC) film structure on a substrate. In some embodiments, the methods may comprise: depositing a first TiAlC film on the substrate utilizing at least one first unit deposition cycle of a first cyclical deposition process at a first growth rate per cycle (GPC), and depositing a second TiAlC film over the first TiAlC film utilizing at least one second unit deposition cycle of a second cyclical deposition process at a second growth rate per cycle, wherein the first growth rate per cycle is greater than the second growth rate per cycle.

A non-limiting example embodiment of a cyclical deposition process may include atomic layer deposition (ALD), wherein ALD is based on typically self-limiting reactions, whereby sequential and alternating pulses of precursors are used to deposit about one atomic (or molecular) monolayer of material per deposition cycle. The deposition conditions and precursors are typically selected to provide self-saturating reactions, such that an absorbed layer of one precursor leaves a surface termination that is non-reactive with the gas phase reactants of the same reactants. The substrate is subsequently contacted with a different precursor that reacts with the previous termination to enable continued deposition. Thus, each cycle of alternated pulses typically leaves no more than about one monolayer of the desired material. However, as mentioned above, the skilled artisan will recognize that in one or more ALD cycles more than one monolayer of material may be deposited, for example, if some gas phase reactions occur despite the alternating nature of the process.

In a cyclical deposition process utilized for the deposition of a titanium aluminum carbide (TiAlC) film, one deposition cycle, i.e., a unit deposition cycle, may comprise exposing the substrate to a first vapor phase reactant, removing any unreacted first reactant and reaction byproducts from the reaction chamber, and exposing the substrate to a second vapor phase reactant, followed by a second removal step. In some embodiments of the disclosure, the first vapor phase reactant may comprise a titanium precursor and the second vapor phase reactant may comprise both a carbon component and an aluminum component, such as, a metalorganic aluminum precursor, for example.

Precursors may be separated by inert gases, such as argon (Ar) or nitrogen (N₂), to prevent gas-phase reactions between reactants and enable self-saturating surface reactions. In some embodiments, however, the substrate may be moved to separately contact a first vapor phase reactant and a second vapor phase reactant. Because the reactions self-saturate, strict temperature control of the substrates and precise dosage control of the precursors may not be required. However, the substrate temperature is preferably such that an incident gas species does not condense into monolayers nor decompose on the surface. Surplus chemicals and reaction byproducts, if any, are removed from the substrate surface, such as by purging the reaction space or by moving the substrate, before the substrate is contacted with the next reactive chemical. Undesired gaseous molecules can be effectively expelled from a reaction space with the help of an inert purging gas. A vacuum pump may be used to assist in the purging.

Reactors capable of being employed to deposit TiAlC film structures may include ALD reactors, as well as CVD reactors, configured to provide the precursors. According to some embodiments, a showerhead reactor may be used. According to some embodiments, cross-flow, batch, minibatch, or spatial ALD reactors may be used.

In some embodiments of the disclosure, a batch reactor may be used. In some embodiments, a vertical batch reactor may be used. In other embodiments, a batch reactor comprises a minibatch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 or fewer wafers. In some embodiments in which a batch reactor is used, wafer-to-wafer non-uniformity is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

The cyclical deposition processes described herein may optionally be carried out in a reactor or reaction chamber connected to a cluster tool. In a cluster tool, because each reaction chamber is dedicated to one type of process, the temperature of the reaction chamber in each module can be kept constant, which improves the throughput compared to a reactor in which the substrate is heated up to the process temperature before each run. Additionally, in a cluster tool, it is possible to reduce the time to pump the reaction chamber to the desired process pressure levels between substrates. In some embodiments of the disclosure, two or more TiAlC cyclical deposition processes as disclosed herein may be performed in a cluster tool comprising multiple reaction chambers, wherein each individual reaction chamber may be utilized to expose the substrate to an individual precursor gas/plasma chemistry and the substrate may be transferred between different reaction chambers for exposure to multiple precursors gases and/or plasma chemistries, the transfer of the substrate being performed under a controlled ambient to prevent oxidation/contamination of the substrate. In some embodiments of the disclosure, each individual reaction chamber may be configured to heat the substrate to a different temperature.

A stand-alone reactor may be equipped with a load-lock. In that case, it may not be necessary to cool down the reaction chamber between each run.

In some embodiments, the cyclical deposition process may be a hybrid ALD/CVD or a cyclical CVD process. For example, in some embodiments, the growth rate of the ALD process may be low compared with a CVD process. One approach to increase the growth rate may be that of operating at a higher substrate temperature than that typically employed in an ALD process, resulting in some portion of a chemical vapor deposition process, but still taking advantage of the sequential introduction of precursors, such a process may be referred to as cyclical CVD. In some embodiments, a cyclical CVD process may comprise the introduction of two or more precursors into the reaction chamber wherein there may be a time period of overlap between the two or more precursors in the reaction chamber resulting in both an ALD component of the deposition and a CVD component of the deposition. For example, a cyclical CVD process may comprise the continuous flow of a one precursor and the periodic pulsing of a second precursor into the reaction chamber.

According to some embodiments of the disclosure, two or more cyclical deposition processes may be used to deposit a titanium aluminum carbide (TiAlC) film structure on a substrate, such as an integrated circuit work piece. In some embodiments, of the disclosure, a unit deposition cycle of the cyclical deposition processes may comprise two distinct deposition steps or stages. In a first stage of the unit deposition cycle (“the titanium stage”), the substrate surface on which deposition is desired may be contacted with a first vapor phase reactant comprising a titanium precursor which chemisorbs on to the surface of the substrate, forming no more than about one monolayer of reactant species on the surface of the substrate. In a second stage of the deposition (“the aluminum/carbon stage”), the substrate surface on which deposition is desired may be contacted with a second vapor phase reactant comprising an aluminum component and a carbon component, i.e., the aluminum/carbon precursor, wherein a TiAlC film may be deposited due to the reaction between the first vapor phase reactant and the second vapor phase reactant.

In some embodiments of disclosure, two or more cyclical deposition processes may be utilized to deposit a titanium aluminum carbide (TiAlC) film structure on a substrate. As a non-limiting example, methods for depositing a titanium aluminum carbide (TiAlC) film structure may comprise depositing a first TiAlC film utilizing a first cyclical deposition process and a second TiAlC film utilizing a second cyclical deposition process, wherein the first growth rate per cycle is greater than the second growth rate pre cycle.

An exemplary titanium aluminum carbide (TiAlC) film structure deposition process may be understood with reference to FIG. 1 which illustrates an exemplary deposition process 100.

In more detail, the exemplary titanium aluminum carbide (TiAlC) film structure deposition process 100 may commence with a process block 110 which comprises, providing a substrate into a reaction chamber and heating the substrate to a desired deposition temperature. The reaction chamber utilized for the deposition may be an atomic layer deposition reaction chamber, or a chemical vapor deposition reaction chamber, or any of the reaction chambers as previously described herein.

In some embodiments of the disclosure, the substrate may be heated to a desired deposition temperature for the subsequent cyclical deposition processes. For example, the substrate may be heated to a substrate temperature (i.e., deposition temperature) of less than 500° C., or less than 450° C., or less than 400° C., or less than 350° C., or less than 300° C., or less than 250° C., or less than 200° C., or even less than 100° C. In some embodiments of the disclosure, the substrate temperature (i.e., the deposition temperature) may be between 100° C. and 700° C., or between 200° C. and 500° C., or even between 400° C. and 450° C.

In some embodiments of the disclosure, the deposition temperature may be maintained during the subsequent two or more cyclical deposition processes utilized for depositing the titanium aluminum carbide (TiAlC) film structure. For example, in some embodiments, the exemplary deposition process 100 may comprise a first cyclical deposition process (process block 120) for depositing a first TiAlC film, and a second cyclical deposition process (process block 130) for depositing a second TiAlC, and the deposition temperature may be maintained substantially constant during both the first cyclical deposition process (process block 120) and second cyclical deposition process (process block 130). In other words, in some embodiments, the first cyclical deposition process and the second cyclical deposition process are performed at the same deposition temperature.

In alternative embodiments, the deposition temperature may be altered between the first cyclical deposition process (process block 120) and the second cyclical deposition process (process block 130). For example, the exemplary process 100 for depositing a titanium aluminum carbide (TiAlC) film structure may be performed utilizing a cluster tool and the first cyclical deposition process (process block 120) may be performed in a first reaction chamber associated with the cluster tool at a first deposition temperature and the second cyclical deposition process (process block 130) may be performed in a second reaction chamber associated with the cluster tool at a second deposition temperature, wherein the second deposition temperature is different from the first deposition temperature.

In addition to achieving a desired deposition temperature, i.e., a desired substrate temperature, the exemplary deposition process 100 (FIG. 1) may also regulate the pressure within the reaction chamber during the two or more cyclical deposition processes to obtain a desired titanium aluminum carbide (TiAlC) film structure. For example, in some embodiments of the disclosure, the exemplary deposition process 100 may be performed within a reaction chamber regulated to a pressure of less than 300 Torr, or less than 200 Torr, or less than 100 Torr, or less than 50 Torr, or less than 25 Torr, or less than 15 Torr, or less than 10 Torr, or less than 5 Torr, or even less than 2 Torr. In some embodiments, the pressure within the reaction chamber during the deposition of the titanium aluminum carbide (TiAlC) film structure may be regulated at a pressure between 1 Torr and 300 Torr, or between 1 Torr and 100 Torr, or between 2 Torr and 5 Torr. In some

In some embodiments of the disclosure, the chamber pressure (i.e., deposition pressure) may be maintained during the subsequent two or more cyclical deposition processes utilized for depositing the titanium aluminum carbide (TiAlC) film structure. For example, in some embodiments, the exemplary deposition process 100 may comprise a first cyclical deposition process (process block 120) for depositing a first TiAlC film and a second cyclical deposition process (process block 130) for depositing a second TiAlC and the deposition pressure may be maintained substantially constant during both the first cyclical deposition process (process block 120) and second cyclical deposition process (process block 130). In other words, in some embodiments, the first cyclical deposition process and the second cyclical deposition process are performed at the same deposition pressure.

Once the substrate has been heated to a desired deposition temperature and the pressure within the reaction chamber has been regulated to a desired level, the exemplary deposition process 100 may continue by performing two or more cyclical deposition processes employed for depositing two or more titanium aluminum carbide (TiAlC) films which together make up a titanium aluminum carbide (TiAlC) film structure. The exemplary deposition process 100 (FIG. 1) utilizes two cyclical deposition processes, i.e., a first cyclical deposition process (the process block 120) with a first growth rate per cycle, and the second cyclical deposition process (the process block 130) with a second growth rate per cycle, wherein the first growth rate per cycle is greater than the second growth rate per cycle.

In some embodiments, the first cyclical deposition process (process block 120) and the second cyclical deposition process (process block 130) may both deposit a titanium aluminum carbide film but at differing growth rates per cycle. Therefore, the first cyclical deposition cycle (process block 120) and the second cyclical deposition cycle (process block 130) may comprise cyclical deposition processes with differing process parameters. For example, the cyclical deposition process parameters may include, but are not limited to, deposition temperature, deposition (chamber) pressure, precursor dose, precursor flow, precursor contacting time period with the substrate, purge time period, selection of titanium precursor, and selection of metalorganic aluminum precursor. In some embodiments of the disclosure, the first cyclical deposition process (process block 120) and the second cyclical deposition process (process block 130) may comprise cyclical deposition processes with associated process parameters that differ by a single change in process parameters between the first cyclical deposition process and the second cyclical deposition process. In some embodiments of the disclosure, the single modification in process parameters between the first cyclical deposition process and the second cyclical deposition process may comprise a modification of one parameter selected from the group comprising: precursor dose, precursor flow, precursor contacting time period with the substrate, selection of the titanium precursor, or selection of the metalorganic aluminum precursor. In particular embodiments of the disclosure, a single modification to the process parameters between the first cyclical deposition process and the second cyclical deposition process comprises the selection of the metalorganic aluminum precursor, wherein the first cyclical deposition process utilizes a first metalorganic aluminum precursor, and the second cyclical deposition process utilizes a second metalorganic aluminum precursor different from the first metalorganic aluminum precursor.

It should be appreciated, the methods of the disclosure may be expanded beyond the two cyclical deposition processes illustrated in the exemplary process 100 (FIG. 1) to the n^(th) number of cyclical deposition process (where n is greater than or equal to 2), wherein each n^(th) cyclical deposition process deposits a titanium aluminum carbide film with a different growth rate per cycle compared to the n^(th)−1 cyclical deposition process and n^(th)+1 cyclical deposition processes by modification of the cyclical deposition parameters between subsequent cyclical deposition processes.

The exemplary deposition process 100 (FIG. 1) may continue by means of a process block 120 which comprises, depositing a first TiAlC film on the substrate utilizing at least one first unit deposition cycle of a first cyclical deposition process at a first growth rate per cycle.

In more detail, the first cyclical deposition cycle (process block 120) and its constituent sub-process blocks are illustrated in FIG. 2. The first cyclical deposition cycle 120 may commence with a cyclical deposition phase 205 by means of a sub-process block 200 which comprising, contacting the substrate with a titanium precursor.

In some embodiments of the disclosure, the titanium precursor may comprise a titanium halide precursor, such as, for example, a titanium chloride precursor, a titanium iodide precursor, or a titanium bromide precursor. As a non-limiting example, the titanium halide precursor may comprise, titanium tetrachloride (TiCl₄), or titanium tetraiodide (TiI₄).

In some embodiments of the disclosure, the titanium precursor may comprise a metalorganic titanium precursor, i.e., a metalorganic precursor comprising a titanium element. For example, the metalorganic titanium precursor may comprise at least one of: tetrakisdimethylamino titanium (TDMAT), tetrakisdiethylamino titanium (TDEAT), pentamethylcyclopentadienyltrimethoxy titanium (CpMe₅Ti(OMe)₃), titanium methoxide (Ti(OMe)₄), titanium ethoxide (Ti(OEt)₄), titanium isopropoxide (Ti(OPr)₄), or titanium butoxide (Ti(OBu)₄). Metalorganic titanium precursors are described in U.S. Pat. No. 9,062,390, issued to Blomberg, and incorporated by reference herein.

In some embodiments of the disclosure, contacting the substrate with a titanium precursor may comprise contacting the substrate with the titanium precursor for a time period of between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. In addition, during the contacting of the substrate with the titanium precursor, the flow rate of the titanium precursor may be less than 2000 sccm, or less than 500 sccm, or less than 100 sccm, or between 1 to 2000 sccm, or between 5 to 1000 sccm, or even between 10 to 500 sccm.

The cyclical deposition phase 205 of the first cyclical deposition process 120 (FIG. 2) may continue by purging the reaction chamber. For example, excess titanium precursor and reaction byproducts (if any) may be removed from the surface of the substrate by introducing an inert purge gas and exhausting the reaction chamber with the aid of a vacuum pump in fluid communication with the reaction chamber. The purge process may comprise a purge cycle, wherein the substrate surface is purged for a time period of less than 5 seconds, or less than 3 seconds, or even less than 2 seconds.

Upon purging the reaction chamber the first cyclical deposition process 120 (FIG. 2) may continue by means of a sub-process block 210 which comprises, contacting the substrate with a first metalorganic aluminum precursor.

In some embodiments of the disclosure, the first metalorganic aluminum precursor may comprise at least one of: trimethylaluminum (TMA), triethylaluminum (TEA), dimethylaluminum hydride (DMAH), dimethylethylaminealane (DMEAA), trimethylaminealane (TEAA), tritertbutylaluminum (TTBA), or N-methylpyrroridinealance (MPA).

In some embodiments of the disclosure, contacting the substrate with the first metalorganic aluminum precursor may comprise, contacting the substrate with the first metalorganic aluminum precursor for a time period of between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. In addition, during the contacting of the substrate with the first metalorganic aluminum precursor, the flow rate of the first metalorganic aluminum precursor may be less than 2000 sccm, or less than 500 sccm, or less than 100 sccm, or between 1 sccm to 2000 sccm, or between 5 sccm to 1000 sccm, or even between 10 sccm to 500 sccm.

In some embodiments of the disclosure, contacting the substrate with the first metalorganic aluminum precursor may comprise two or more micro pulsing processes. For example, each micro pulsing process may comprise: contacting the substrate with a micro pulse of the first metalorganic aluminum precursor, and purging the reaction chamber with a micro purge, wherein each of the micro pulses of the first metalorganic aluminum precursor provides a substantially constant concentration of the first metalorganic aluminum precursor into the reaction chamber. In some embodiments, each micro pulse of the first metalorganic aluminum precursor has a pulse time period between 0.05 seconds and 10 seconds, and each micro purge has a purge time period of between 0.1 seconds and 10 seconds. Further information relating to micro pulsing precursors is described in U.S. Patent Publication 2019/0221433 from Raisanen et. al, entitled “Method for depositing a material film on a substrate within a reaction chamber by a cyclical deposition process and related device structures” the entire contents of which is incorporated by reference herein.

Upon contacting the substrate with the first metalorganic aluminum precursor, the first cyclical deposition process 120 may proceed by purging the reaction chamber, as described previously herein and therefore not repeated in the interest of brevity.

Upon completion of the purge of the first metalorganic aluminum precursor (and any reaction byproducts) from the reaction chamber, the cyclic deposition phase 205 of the first cyclical deposition process 120 (FIG. 2) may proceed by means of a decision gate 220, the decision gate 220 being dependent on the thickness of the first TiAlC film deposited. For example, if the first TiAlC film is deposited at an insufficient thickness for a desired device application, then the cyclical deposition phase 205 may be repeated by returning to the sub-process block 200 and continuing through a further deposition cycle, wherein a first unit deposition cycle may comprise: contacting the substrate with a titanium precursor (sub-process block 200), purging the reaction chamber, contacting the substrate with a first metalorganic aluminum precursor (sub-process block 210), and again purging the reaction chamber. A first unit deposition cycle of the first cyclical deposition process 120 may be repeated one or more times until a desired thickness of the first TiAlC film is deposited over the substrate.

It should be appreciated that in some embodiments of the disclosure, the order of contacting of the substrate with the titanium precursor and the first metalorganic aluminum precursor may be such that the substrate is first contacted with the first metalorganic aluminum precursor followed by the titanium precursor. In addition, in some embodiments, the cyclical deposition phase 205 of the first cyclical deposition process 120 (FIG. 2) may comprise, contacting the substrate with the titanium precursor one or more times prior to contacting the substrate with the first metalorganic aluminum precursor one or more times. In addition, in some embodiments, the cyclical deposition phase 205 of the first cyclical deposition process 120 may comprise, contacting the substrate with the first metalorganic aluminum precursor one or more times prior to contacting the substrate with the titanium precursor one or more times.

In some embodiments, the first cyclical deposition process 120 may deposit a first TiAlC film at a first growth rate per cycle (Å/cycle). In some embodiments, the first growth rate per cycle may be less than 10 Å/cycle, or less than 8 Å/cycle, or less than 6 Å/cycle, or even less than 5 Å/cycle. In some embodiments, the first growth rate per cycle may between 5 Å/cycle and 10 Å/cycle, or between 6 Å/cycle and 9 Å/cycle, or between 6 Å/cycle and 7 Å/cycle.

In some embodiments, the first TiAlC film may be deposited to an average film thickness of less than 50 Å, or less than 40 Å, or less than 30 Å, or less than 20 Å, or less than 10 Å, or even less than 5 Å. In some embodiments, the first TiAlC film may be deposited to an average film thickness of between 1 Å to 50 Å, or between 5 Å to 20 Å, or between 5 Å to 10 Å.

In some embodiments of the disclosure, the first TiAlC film may be deposited by performing at least one first unit deposition cycle of the first cyclical deposition process. In some embodiments, the first unit deposition cycle may be performed less than five (5) times (i.e., less than 5 deposition cycles), or less than four (4) time (i.e., less than 4 deposition cycles), or less than three (3) time (i.e., less than 3 deposition cycles), or less than two (2) times (i.e., less than 2 deposition cycles), or may even be performed once (i.e., a single (1) deposition cycle). In some embodiments of the disclosure, the first unit deposition cycle of the first cyclical deposition process may be performed for between 1 cycle to 5 cycles, or between 1 to 3 cycles, or between 1 to 2 cycles. In particular embodiments of the disclosure, the first growth rate per cycle may be equal to or less than 10 Å/cycle and the first unit deposition cycle may be performed less than twice (2) (i.e., less than 2 deposition cycles), or even performed once for a single (1) deposition cycle.

In some embodiments, the first TiAlC film may have an average r.m.s. surface roughness (R_(a)) of less than 5 Å, or less than 3 Å, or even less than 2 Å. For example, the average r.m.s. surface roughness (R_(a)) may be determined by an atomic force microscopy (AFM) measurement over a surface area of 100 microns×100 microns.

In some embodiments of the disclosure, the first TiAlC film may be deposited with an atomic-% of aluminum between 10 atomic-% and 50 atomic-%, or between 20 atomic-% and 45 atomic-%, or between 30 atomic-% and 40 atomic-%. In some embodiments, the first TiAlC film may be deposited with an atomic-% of aluminum less than 50 atomic-%, or less than 45 atomic-%, or less than 40 atomic-%, or less than 35 atomic-%, or less than 30 atomic-%, or less than atomic-%, or less than 20 atomic-%. In the example embodiments given herein, the atomic-% of aluminum within the first TiAlC film maybe determined utilizing Ruther backscattering spectrometry (RBS).

Upon completion of depositing the first TiAlC film to the desired thickness, the first cyclical deposition process 120 (FIG. 2) may exit by means of a sub-process block 230.

Upon exiting the first cyclical deposition process, the exemplary deposition process 100 (FIG. 1) for depositing a titanium aluminum carbide (TiAlC) film structure may continue by means of a process block 130 comprising, depositing a second TiAlC film over the first TiAlC film utilizing at least one second unit deposition cycle of a second cyclical deposition process at a second growth rate per cycle (process block 130).

In more detail, the second cyclical deposition cycle (process block 130) and its constituent sub-process blocks are illustrated in FIG. 3. The second cyclical deposition cycle 130 may commence with a cyclical deposition phase 305 by means of a sub-process block 300 which comprising, contacting the substrate with a titanium precursor. The sub-process block 300 may be substantially similar to the sub-process block 200 as described previously and therefore in the interest of brevity is not repeated here.

The cyclical deposition phase 305 of the second cyclical deposition process 130 (FIG. 3) may continue by purging the reaction chamber as previously described with reference to first cyclical deposition process 120 (FIG. 2) and therefore not repeated here.

Upon purging the reaction chamber the second cyclical deposition process 130 (FIG. 3) may continue by means of a sub-process block 310 which comprises, contacting the substrate with a second metalorganic aluminum precursor.

In some embodiments of the disclosure, the second metalorganic aluminum precursor may comprise at least one of: trimethylaluminum (TMA), triethylaluminum (TEA), dimethylaluminum hydride (DMAH), dimethylethylaminealane (DMEAA), trimethylaminealane (TEAA), tritertbutylaluminum (TTBA), or N-methylpyrroridinealance (MPA).

In some embodiments of the disclosure, the second metalorganic aluminum precursor may be less reactive than the first metalorganic aluminum precursor. In other words, the first metalorganic aluminum precursor may be more reactive than the second metalorganic aluminum precursor.

In some embodiments of the disclosure, the first metalorganic aluminum precursor may comprise a greater number of carbon atoms than the second metalorganic aluminum precursor.

In some embodiments of the disclosure, the first metalorganic aluminum precursor may comprise trimethylaluminum (TEA). In some embodiments, the second metalorganic aluminum precursor may comprise trimethylaluminum (TMA).

In some embodiments of the disclosure, contacting the substrate with the second metalorganic aluminum precursor may comprise, contacting the substrate with the second metalorganic aluminum precursor for a time period of between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. In addition, during the contacting of the substrate with the second metalorganic aluminum precursor, the flow rate of the second metalorganic aluminum precursor may be less than 2000 sccm, or less than 500 sccm, or less than 100 sccm, or between 1 sccm to 2000 sccm, or between 5 sccm to 1000 sccm, or even between 10 sccm to 500 sccm.

In some embodiments of the disclosure, contacting the substrate with the second metalorganic aluminum precursor may comprise two or more micro pulsing processes, as previously disclosed herein. In some embodiments, each micro pulse of the second metalorganic aluminum precursor has a pulse time period between 0.05 seconds and 10 seconds, and each micro purge has a purge time period of between 0.1 seconds and 10 seconds.

Upon contacting the substrate with the second metalorganic aluminum precursor, the second cyclical deposition process 130 may proceed by purging the reaction chamber, as described previously herein and therefore not repeated in the interest of brevity.

Upon completion of the purge of the second metalorganic aluminum precursor (and any reaction byproducts) from the reaction chamber, the cyclic deposition phase 305 of the second cyclical deposition process 130 (FIG. 3) may proceed by means of a decision gate 320, the decision gate 320 being dependent on the thickness of the second TiAlC film deposited. For example, if the second TiAlC film is deposited at an insufficient thickness for a desired device application, then the cyclical deposition phase 305 may be repeated by returning to the sub-process block 300 and continuing through a further deposition cycle, wherein a second unit deposition cycle, may comprise: contacting the substrate with a titanium precursor (sub-process block 300), purging the reaction chamber, contacting the substrate with a second metalorganic aluminum precursor (sub-process block 310), and again purging the reaction chamber. A second unit deposition cycle of the second cyclical deposition process 130 may be repeated one or more times until a desired thickness of the second TiAlC film is deposited over the substrate.

As described previously in relation to the first cyclical deposition process, it should be appreciated that in some embodiments, the order of precursors contacting the substrate may be differ from that described above and any conceivable sequence of the contacting sub-processes, purge cycles, and repetitions thereof, is assumed as part of the present disclosure.

In some embodiments, the second cyclical deposition process 130 may deposit a second TiAlC film at a second growth rate per cycle (Å/cycle). In some embodiments, the second growth rate per cycle may be less than the first growth rate per cycle. In other words, the first TiAlC film may be deposited at a first growth rate per cycle and second TiAlC film may be deposited at a second growth rate per cycle, wherein the first growth rate per cycle is greater than the second growth rate per cycle.

In some embodiments of the disclosure, the second growth rate per cycle may be less than 5 Å/cycle, or less than 4 Å/cycle, or less than 3 Å/cycle, or even less than 2 Å/cycle. In some embodiments, the second growth rate per cycle may between 2 Å/cycle and 5 Å/cycle.

In some embodiments, the second TiAlC film may be deposited to an average film thickness of less than 20 Å, or less than 15 Å, or less than 10 Å, or less than 5 Å, or less than 4 Å, or even less than 3 Å. In some embodiments, the second TiAlC film may be deposited to an average film thickness of between 1 Å to 20 Å, or between 2 Å to 15 Å, or between 4 Å to 10 Å.

In some embodiments of the disclosure, the second TiAlC film may be deposited by performing at least one second unit deposition cycle of the second cyclical deposition process. In some embodiments, the second unit deposition cycle may be performed less than three (3) times (i.e., less than 3 deposition cycles), or less than two (2) times (i.e., less than 2 deposition cycles), or even performed once (1) for 1 deposition cycle. In some embodiments of the disclosure, the second unit deposition cycle of the second cyclical deposition process may be performed for between 1 cycle to 3 cycles, or between 1 to 2 cycles. In particular embodiments of the disclosure, the second growth rate per cycle may be equal to or less than 8 Å/cycle and the second unit deposition cycles may be performed for less than 2 cycles, or performed for a single (1) cycle.

In some embodiments, the second TiAlC film may have an average r.m.s. surface roughness (R_(a)) of less than 5 Å, or less than 3 Å, or even less than 2 Å. For example, the average r.m.s. surface roughness (Ra) may be determined by an atomic force microscopy (AFM) measurement over a surface area of 100 microns×100 microns.

In some embodiments of the disclosure, the second TiAlC film may be deposited with an atomic-% of aluminum between 1 atomic-% and 20 atomic-%, or between 2 atomic-% and 15 atomic-%, or between 5 atomic-% and 12 atomic-%. In some embodiments, the second TiAlC film may be deposited with an atomic-% of aluminum less than 20 atomic-%, or less than 15 atomic-%, or less than 12 atomic-%, or less than 10 atomic-%, or less than 8 atomic-%, or less than 6 atomic-%, or even less than 4 atomic-%. In the example embodiments given herein, the atomic-% of aluminum within the second TiAlC film maybe determined utilizing Ruther backscattering spectrometry (RBS).

Upon completion of depositing the second TiAlC film to the desired thickness, the second cyclical deposition process 130 (FIG. 3) may exit by means of a sub-process block 330.

Upon exiting the second cyclical deposition process, the exemplary process 100 (FIG. 1) for depositing a titanium aluminum carbide (TiAlC) film structure may exit by means of a process block 140 and the titanium aluminum carbide (TiAlC) film structure, comprising both the first TiAlC film and the second TiAlC film may be subjected to further device fabrication processes.

In some embodiments of the disclosure, the titanium aluminum carbide (TiAlC) film structure may have an average film thickness of less than 50 Å, or less than 40 Å, or less than 30 Å, or less than 20 Å, or even less than 10 Å. In some embodiments, the titanium aluminum carbide (TiAlC) film structure has an average film thickness between 10 Å and 50 Å, or between 15 Å and 40 Å, or between 20 Å and 30 Å.

In some embodiment, the titanium aluminum carbide (TiAlC) film structure may have an average r.m.s. surface roughness (R_(a)) of less than 5 Å, or less than 3 Å, or even less than 2 Å. For example, the average r.m.s. surface roughness (Ra) may be determined by an atomic force microscopy (AFM) measurement over a surface area of 100 microns×100 microns.

In some embodiments, the surface roughness of a titanium aluminum carbide (TiAlC) film structure may be expressed as a percentage roughness of the average total thickness of the TiAlC film structure. For example, the percentage surface roughness of the TiAlC film structure may be less than 10%, or less than 8%, or less 5%, or less than 3%, or even less than 1%. As a non-limiting example, a TiAlC film structure having an average film thickness of less than 25 Å with a r.m.s. surface roughness (R_(a)) of less than 2 Å and a corresponding percentage surface roughness of less than 8%.

The cyclical deposition processes disclosed herein and the associated titanium aluminum carbide (TiAlC) film structures may be utilized in a multitude of applications. As a non-limiting example, the TiAlC film structures of the present disclosure may be employed as a portion of a metal gate stack (i.e., the gate electrode) to a semiconductor device, such as, a NMOS semiconductor device. For example, for NMOS devices structures, the effective work function of the metal gate stack is preferably less than approximately 4.3 eV to be compatible with the barrier height of the semiconductor material.

In more detail, FIG. 4A illustrates a semiconductor structure 400 including a substrate 405. The substrate 405 comprises a semiconductor body 402, which in this example encompasses a p-type semiconductor body 402 (e.g., p-type silicon), a p-type channel region 404, and n-type source/drain regions 406/408. Disposed over the p-type channel region 404 is a gate dielectric stack 410 which in this non-limiting example comprises: a silicon oxide interface film 412 disposed directly on the p-type channel region 404, and a high-k dielectric film 414 disposed directly over the silicon oxide interface film 412. In some embodiments, the high-k dielectric film 414 may comprise at least one of hafnium oxide (HfO₂), tantalum oxide (Ta₂O₅), zirconium oxide (ZrO₂), titanium oxide (TiO₂), hafnium silicate (HfSiO_(x)), lanthanum oxide (La₂O₃), or mixtures/laminates thereof. In particular embodiments, the high-k dielectric film 414 may comprise a hafnium oxide film, such as, HfO₂, for example.

The substrate 405 may also comprise an additional option film 416 (illustrated with a dashed outline in FIG. 4A) which may be disposed directly over the upper surface of the high-k dielectric film 414. The additional optional film 416 may constitute a barrier film comprising, for example, a transition metal nitride film (e.g., a titanium nitride film) and may be employed to prevent species from a subsequent metal gate stack (disposed over the gate dielectric stack 410) from diffusing into the high-k dielectric film 414. The additional optional film 416 may have an exposed surface 418.

FIG. 4B illustrates a semiconductor structure 415 which comprises the semiconductor structure 400 (of FIG. 4A) post the cyclical deposition of a first titanium aluminum carbide (TiAlC) film 420 according to the embodiments of the disclosure.

Therefore, in some embodiments the first TiAlC film 420 may be deposited over a high-k dielectric film 414. In some embodiments, the methods of the disclosure may further comprise depositing a transition metal nitride film 416 directly over the high-k dielectric film 414 prior to depositing the first TiAlC film 420 directly over the transition metal nitride film 416. In particular embodiments, the methods of the disclosure may comprise, depositing a titanium nitride film 416 directly over the high-k dielectric film 414 prior to depositing the first TiAlC film 420 directly over the titanium nitride film. In some embodiments, both the transition metal nitride film 416 and the first TiAlC film 420 may be deposited by cyclical deposition processes within the same reaction chamber, e.g., within a reaction chamber configured for ALD processes or cyclical chemical vapor deposition processes.

In alternative embodiments, the optional transition metal nitride film 416 may be omitted and the first TiAlC film 420 may be deposited directly on the high-k dielectric film 414. In such examples (not illustrated), a deposition surface of the substrate comprises a high-k dielectric film and the first TiAlC film 420 may be deposited directly over the high-k dielectric film 414.

FIG. 4C illustrates a semiconductor structure 430 which comprises the semiconductor structure 415 (of FIG. 4B) post the cyclical deposition of a second titanium aluminum carbide (TiAlC) film 422 according to the embodiments of the disclosure.

As illustrated in FIG. 4C, in some embodiments, the second TiAlC film 422 may be deposited over the first TiAlC film 420. In particular embodiments (as illustrated in FIG. 4C), the second TiAlC film 422 may be deposited directly over the first TiAlC film 420. In alternative embodiments, there may be any number of intervening layers deposited and disposed between the first TiAlC film 420 and the second TiAlC film 422.

In some embodiments of the disclosure, the first TiAlC film 420 may have a greater atomic-% of aluminum than the second TiAlC film 422. As a non-limiting example, the first TiAlC film 420 may have an atomic-% of aluminum between 20 atomic-% and 50 atomic-%, or between 30 atomic-% and 40 atomic-%, or even 40 atomic-%. In contrast, the second TiAlC film 422 may have an atomic-% of aluminum between 1 atomic-% and 20 atomic-%, or between 2 atomic-% and 15 atomic-%, or between 5 atomic-% and 12 atomic-%, or even approximately 10 atomic-%. As disclosed previously, the atomic-% of aluminum (and other species) may be determined utilizing Rutherford backscattering spectrometry (RBS), for example.

In some embodiments of the disclosure, the effective work function of the metal gate stack (of which the TiAlC film structure 425 is a portion) may be determined in part by the composition of the TiAlC film structure proximate to the high-k dielectric film 414. For example, a first TiAlC film 420 with a greater atomic-% of aluminum may be desirable proximate to the high-k dielectric film 414 and a second TiAlC film 422 with a lesser atomic-% of aluminum may be desirable distal to the high-k dielectric film 414. Therefore, in some embodiments, a first TiAlC film may be disposed proximate to a high-k dielectric film 414 with an atomic-% of aluminum between 20 atomic-% and 50 atomic-% and a second TiAlC film may be disposed distal to a high-k dielectric film 414 with an atomic-% of aluminum between 1 atomic-% and 20 atomic-%.

In addition, in some embodiments, the growth rate per cycle of a TiAlC film deposited by a cyclical deposition process with fixed process parameters may be at least partially dependent on the atomic-% of aluminum in the TiAlC film being deposited. For example, a TiAlC film with a high atomic-% of aluminum, e.g., between 20 atomic-% and 50 atomic-%, may have a higher growth rate per cycle than a TiAlC film with a lower atomic-% of aluminum, e.g., between 1 atomic-% and 20 atomic-%, for a single cyclical deposition process with fixed process parameters. Therefore, to enable deposition of a TiAlC film structure with both a high atomic-% of aluminum proximate to the high-k dielectric film and a reduced, controllable growth rate per cycle for a higher order of thickness control, the embodiments of the current of the disclosure employ two or more cyclical deposition process with differing growth rates per cycle. For example, a high growth rate per cycle (e.g., between 5 Å/cycle and 10 Å/cycle) first cyclical deposition process may be utilized to deposit a first TiAlC film proximate to a high-k dielectric film and a low growth rate per cycle (e.g., between 2 Å/cycle and 4 Å/cycle) may be utilized to deposit a second TiAlC film distal to a high-k dielectric film.

As a non-limiting example, a first TiAlC film 420 may be deposited proximate to a high-k dielectric film at a growth rate per cycle between 5 Å/cycle and 10 Å/cycle to a an average film thickness of less than 20 Å employing a first metalorganic aluminum precursor comprising trimethylaluminum (TEA) at a deposition temperature of less than 450° C. In addition, a second TiAlC film 422 may be deposited over the first TiAlC film 420 and distal to the high-k dielectric film at a growth rate per cycle between 2 Å/cycle and 4 Å/cycle to an average film thickness of less than 10 Å employing a second metalorganic aluminum precursor comprising trimethylaluminum (TMA).

In a particular non-limiting example, the average film thickness target for a titanium aluminum carbide (TiAlC) film structure may be approximately 25 Å. In such an embodiment, the first unit cycle of the first cyclical deposition process may performed twice (2) to cyclically deposit a first TiAlC film with an average film thickness of 20 Å (i.e., with a first growth rate per cycle of approximately 10 Å/cycle). Subsequently, the second unit cycle of the second cyclical deposition process may be performed once (1) to deposit a second TiAlC film with an average film thickness of 5 Å (i.e., with a second growth rate per of approximately 5 Å/cycle), giving a total average film thickness for the TiAlC film structure, comprising both the first and second TiAlC films, of approximately 25 Å.

FIG. 4D illustrates a semiconductor structure 445 which comprises the semiconductor structure 430 (of FIG. 4C) post deposition of a capping film 424, such as a transition metal nitride (e.g., titanium nitride), and a low resistivity metal film 426. As illustrated in FIG. 4D, the complete gate stack 440 comprises both the dielectric gate stack 410 and the metal gate stack 430, the metal gate stack comprising a TiAlC film structure deposited according to the embodiments of the present disclosure. In some embodiments, the gate stack 440 has an effective work function of less than 4.3 eV, or less than 4.2 eV, or less than 4.1 eV, or even less than 4.0 eV. In some embodiments, the gate stack 440 has an effective work function of less than 4.2 eV, wherein the gate stack 440 comprises a first TiAlC film proximate to the high-k dielectric film with an atomic-% of aluminum between 20 atomic-% and 50 atomic-% and a second TiAlC film disposed over the first TiAlC (and distal to a high-k dielectric film 414) with an atomic-% of aluminum between 1 atomic-% and 20 atomic-%.

In some embodiments of the disclosure, a TiAlC film structure deposited according to the embodiments of the current disclosure may be utilized as at least portion of a metal gate stack disposed on or over a semiconductor device structure such as, but not limited to, a planar field effect transistor, a finFET, or a gate all around (GAA) transistor.

As previously disclosed, it should be appreciated, the methods of the disclosure are not limited to a first cyclical deposition cycle with a first growth rate per cycle and second cyclical deposition with a second growth rate per cycle, but rather the methods of the disclosure may be expanded to the n^(th) number of cyclical deposition process (where n is greater than or equal to 2), wherein the n^(th) cyclical deposition process deposits a titanium aluminum carbide film with a different growth rate per cycle compared to the n^(th)−1 cyclical deposition process and the n^(th)+1 cyclical deposition processes by modification of the cyclical deposition parameters between subsequent cyclical deposition processes.

For example, the embodiment of the disclosure may be utilized to a deposit a TiAlC film structure comprising three TiAlC films, wherein the growth rate per cycle decreases with each subsequent TiAlC film deposition, i.e., the growth rate per cycle of the third TiAlC film is less than the growth rate per cycle of the second TiAlC film, and the growth rate per cycle of the second TiAlC film is less than the growth rate per cycle of the first TiAlC film.

The embodiments of the disclosure may also comprise semiconductor deposition apparatus configured for depositing the titanium aluminum carbide film structures of the present disclosure. In some embodiments, the semiconductor deposition apparatus may comprise a reaction chamber configured for performing cyclical deposition process, such as, for example, reaction chambers configured for performing atomic layer deposition and/or cyclical chemical vapor deposition. In such embodiments, the semiconductor deposition apparatus may include three of more precursor source vessels fluid connected to a reaction chamber. For example, the three or more precursor source vessel may comprise: a titanium precursor source, a first metalorganic aluminum precursor source, and a second metalorganic aluminum precursor source.

The example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention, which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combination of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims. 

What is claimed is:
 1. A method for depositing a titanium aluminum carbide (TiAlC) film structure on a substrate, the method comprising: depositing a first TiAlC film on the substrate utilizing at least one first unit deposition cycle of a first cyclical deposition process at a first growth rate per cycle; and depositing a second TiAlC film over the first TiAlC film utilizing at least one second unit deposition cycle of a second cyclical deposition process at a second growth rate per cycle; wherein the first growth rate per cycle is greater than the second growth rate per cycle.
 2. The method of claim 1, wherein the first unit deposition cycle and the second unit deposition cycle comprise: contacting the substrate with a titanium precursor, and contacting the substrate with a metalorganic aluminum precursor.
 3. The method of claim 2, wherein the first cyclical deposition process utilizes a first metalorganic aluminum precursor as the metalorganic aluminum precursor and the second cyclical deposition process utilizes a second metalorganic aluminum precursor different from the first metalorganic aluminum precursor as the metalorganic aluminum precursor.
 4. The method of claim 3, wherein the first metalorganic aluminum precursor is more reactive than the second metalorganic aluminum precursor.
 5. The method of claim 3, wherein the first metalorganic aluminum precursor contains a greater number of carbon atoms than the second metalorganic aluminum precursor.
 6. The method of claim 3, wherein the first metalorganic aluminum precursor comprises triethylaluminum (TEA).
 7. The method of claim 3, wherein the second metalorganic aluminum precursor comprises trimethylaluminum (TMA).
 8. The method of claim, 1 wherein the first TiAlC film has a greater atomic-% of aluminum than the second TiAlC film.
 9. The method of claim 1, wherein the first TiAlC film has an atomic-% of aluminum between 20 atomic-% and 50 atomic-%.
 10. The method of claim 9, wherein the first TiAlC film has an atomic-% of aluminum between 30 atomic-% and 40 atomic-%/
 11. The method of claim 1, wherein the second TiAlC film has an atomic-% of aluminum between 5 atomic-% and 15 atomic-%.
 12. The method of claim 1, wherein the first growth rate per cycle is between 5 Å/cycle and 10 Å/cycle.
 13. The method of claim 1, wherein the second growth rate per cycle is between 2 Å/cycle and 4 Å/cycle.
 14. The method of claim 1, wherein the first TiAlC film has an average surface roughness (Ra) of less than 3 Å.
 15. The method of claim 1, wherein the second TiAlC film has an average surface roughness (Ra) of less than 3 Å.
 16. The method of claim 1, wherein the second TiAlC film is deposited directly over the first TiAlC film.
 17. The method of claim 1, wherein a deposition surface of the substrate comprises a high-k dielectric material and the first TiAlC film is deposited over the high-k dielectric film.
 18. The method of claim 17, wherein the first TiAlC film is deposited directly over the high-k dielectric material.
 19. The method of claim 17, further comprising depositing a transition metal nitride film directly over the high-k dielectric material prior to depositing the first TiAlC film directly over the transition metal nitride film.
 20. The method of claim 1, wherein the titanium aluminum carbide (TiAlC) film structures has an average film thickness of between 20 Å and 50 Å.
 21. The method of claim 1, wherein the deposition temperature is less than 450° C.
 22. The method of claim 1, wherein the titanium aluminum carbide (TiAlC) film structure comprises at least a portion of a metal gate stack disposed on or over a semiconductor device structure.
 23. The method of claim 22, wherein the semiconductor device structure comprises a gate all around (GAA) transistor.
 24. A gate electrode including a titanium aluminum carbide (TiAlC) film structure deposited according to the method of claim
 1. 25. A semiconductor deposition apparatus configured to perform the method of claim
 1. 